Black Effect Pigment

ABSTRACT

This disclosure is directed to a black effect pigment and a method of forming said pigment. The pigment comprises a platy substrate coated with SnO 2  and/or SnO 2  hydrates and Fe 3 O 4  with an optional coating of metal oxides such as SiO 2 , TiO 2 , ZrO 2  and ZnO 2 . The deposition of the SnO 2  and/or SnO 2  hydrates onto the substrate improves the adhesion and prepares the substrate surface for deposition of the iron oxides onto the platy surface, especially mica surfaces. While the pigment may be used in such applications as coating, powder coating, printing ink, plastic, ceramic material, glass, cosmetic formulation, laser marking pigment, pigment composition or dry preparation, the pigment is especially suitable for cosmetic applications.

This application claims the benefit of U.S. Provisional Application No.61/452,804 filed Mar. 15, 2011 herein incorporated entirely byreference.

BACKGROUND

Effect pigments, also known as pearlescent pigments or nacreouspigments, are used to impart a pearlescent luster, metallic lusterand/or multi-color effect approaching iridescent, to a material. Forinstance, black effect pigments based on flake-form substrates are ofparticular interest in cosmetics. One of the primary black effectpigments approved for cosmetic applications includes Fe₃O₄-based effectpigments.

U.S. Pat. Nos. 3,926,659, 7,303,622 and U.S. publication no.2007/0032573 disclose Fe₃O₄ based effect pigments.

Fe₃O₄-based effect pigments tend to be very stable and not subject todecomposition the way many color based pigments, such as carmine are.However, Fe₃O₄-based effect pigments normally do not provide sufficientblackness.

In addition, Fe₃O₄ does not bind well to platy substrates. For example,Fe₃O₄ adhesion to substrates such as mica and perlite is weak.Accordingly, once the Fe₃O₄ coated substrates are subjected tomechanical shear, such as hand mixing of the product in a lacquer, theFe₃O₄ layer or coating is easily removed from the surface of thesubstrate. This removal of Fe₃O₄ coating or layer from the substrate cancause “staining” issues.

Thus, there is an on-going need in the art for black effect pigmentcompositions with improved darkness and improved adhesion to platysubstrates.

SUMMARY

The inventors have discovered that some of these weaknesses inFe₃O₄-based effect pigments, can be addressed by using the variousembodiments disclosed herein.

The primary embodiments of this disclosure are directed to:

-   -   A novel black effect pigment    -   A paint, coating, printing ink, cosmetic formulation, laser        marking, pigment composition or dry preparation, especially a        cosmetic formulation comprising the inventive black effect        pigment,    -   A method of preparing said black effect pigment and    -   A method of increasing the adhesion of Fe₃O₄ to a substrate.

Accordingly, the invention is directed to a black effect pigmentcomprising

-   -   a) at least a partial layer of SnO₂ and/or hydrated SnO₂ on a        substrate,    -   b) at least a partial layer of Fe₃O₄    -   c) and optionally, a further layer of metal oxide, wherein the        partial layer of Fe₃O₄ may further contain ferric hydroxide and        Fe₂O₃.

A paint, coating, printing ink, cosmetic formulation, laser marking,pigment composition or dry preparation, especially a cosmeticformulation comprising the inventive black effect pigment is animportant embodiment of the present disclosure.

A method of preparing the black effect pigment comprises the steps of

-   -   applying a coating or layer of Fe₃O₄ onto an at least partially        coated or layered SnO₂ coated substrate and optionally applying        a further metal oxide coating.

A method of increasing the adhesion of Fe₃O₄ to a substrate comprisingthe steps of

-   -   a) at least partially coating the substrate with SnO₂ and/or        SnO₂ hydrate,    -   b) applying Fe₃O₄ to the at least partially coated substrate of        step a) and    -   c) optionally, applying a further metal oxide coating, wherein        the partial layer of Fe₃O₄ may further contain ferric hydroxide        and Fe₂O₃.

Alterantively, this may be expressed as a method of preparing asubstrate surface for Fe₃O₄ deposition comprising the steps of

-   -   a) at least partially coating the substrate with SnO₂ and/or        SnO₂ hydrate,    -   b) applying Fe₃O₄ to the at least partially coated substrate of        step a) and    -   c) optionally, applying a further metal oxide coating, wherein        the partial layer of Fe₃O₄ may further contain ferric hydroxide        and Fe₂O

BRIEF DESCRIPTION OF THE DRAWINGS

Figures I through IV are representative of tin oxide treated mica uponwhich Fe₃O₄ is deposited. The black spots indicate Fe₃O₄. Pictures I-IVwas taken on a Nikon LV-100 at 400× magnification. Picture V taken at100× magnification.

Figure (I) represents 0.39 wt. % SnO₂ and/or SnO₂ hydrate layer and 39wt. % Fe₃O₄ layer on mica.

Figure (II) represents 3.2 wt. % SnO₂ and/or SnO₂ hydrate layer and 31wt. % Fe₃O₄ layer on mica.

Figure (III) represents 2.6 wt. % SnO₂ and/or SnO₂ hydrate layer and 40wt. % layer of Fe₃O₄ on mica.

Figure (IV) represents 1.92 wt. % SnO₂ and/or SnO₂ hydrate layer and18.4 wt. % layer of Fe₃O₄ on mica.

Figure (V) represents 25 wt. % layer of Fe₃O₄ on mica.

DETAILED DESCRIPTION

Definitions

The term “substrate” for purposes of this disclosure means platyinorganic or organic treated or untreated materials. For example, suchplaty materials may include aluminum oxide, platy glass, perlite,aluminum, natural mica, synthetic mica, bismuth oxychloride, platy ironoxide, platy graphite, platy silica, bronze, stainless steel, naturalpearl, boron nitride, copper flake, copper alloy flake, zinc flake, zincalloy flake, zinc oxide, enamel, china clay, porcelain, titanium oxide,platy titanium dioxide, titanium suboxide, kaolin, zeolites andcombinations thereof.

As defined above the substrate may be treated or untreated. For example,the substrate may be treated with virtually any agent such silicones andcoupling agents. Alternatively, the substrate may be mechanicallytreated to smooth the surface, or plasma or radiation treatments toactivate the surface before application of the at least partial coatingsof SnO₂ and Fe₃O₄.

In a preferred embodiment, the substrate may be selected from the groupconsisting of natural mica, synthetic mica, perlite, platy glass,bismuth oxychloride and aluminum. Mica (natural and synthetic) is ofspecial importance.

The descriptor “platy” as used herein is well understood in the art. Theterm “platy” may be used interchangeably with flake, flake-like,plate-like, platelet and flaky.

When the term black is used this means substantially black.

“Substantially black” means for purposes of this disclosure that theblack color is distinguished by sufficient blackness, that is of low Lvalue, and the “a” and “b” values are around the zero point. The blackmay contain overtones of other colors such as gold, red, green etc.Defined adjustments of the “a” and “b” values enables black interferencepigments having a gold, green red or blue tint to be obtained.

The phrase “at least partial layers or coatings” refers to the SnO₂,Fe₃O₄ or optional metal oxide coating, layers or stacks and means thatthe coating may be incomplete or partial, that is not a completelycontinuous layer covering the total platy surface but only part of theplaty surface.

The disclosures of each and every patent, patent application, andpublication cited herein are hereby incorporated herein by reference intheir entirety.

Substrate

As described above, the platy substrate may be organic or inorganic butis preferably inorganic.

The substrate may be further characterized in a number of ways. Forexample, the platy substrate diameter may range from about 0.1 to about350 microns, preferably about 5 to about 250 microns and most preferablyfrom about 1 to about 150 microns.

The platy substrate may also be a mixture of identical or differentsubstrates, each having different particle sizes. The substrate mixturecan consist of two, three or more different substrates. Preference isgiven to one substrate, say for example natural mica or synthetic mica.

SnO₂

In an important embodiment, the SnO₂ and/or hydrated SnO₂ may partiallyor completely coat the substrate wherein the partially coated orcompletely coated substrate is adjacently and directly coated with atleast a partial coating or layer of Fe₃O₄.

The SnO₂ coating or layer may or may not directly impinge on thesubstrate. However, the SnO₂ coating or layer will directly contact atleast one Fe₃O₄ layer, stack or coating.

Another important embodiment is the platy substrate, especially mica maybe seeded with SnO₂ followed by or with an adjacent TiO₂ layer.Accordingly a TiO₂ layer containing SnO₂ may be used as the adjacentlayer upon which the Fe₃O₄ coating is applied.

It is preferably however, that the SnO₂ coating or layer which impingeson the Fe₃O₄ coating layer is not incorporated into a TiO₂ coating orlayer.

The amount of the SnO₂ or hydrated SnO₂ compound required to bedeposited onto the platy surface can vary. But typically the minimumamount of tin oxide and/or hydrate thereof ranges from at least about0.01 wt. %, preferably 0.1 wt. %, and most preferably about 0.5 wt. %SnO₂ and/or hydrate thereof based on the total weight of the effectpigment.

Accordingly, the amount of SnO₂ and/or SnO₂ hydrate as a wt. percent ofthe effect pigment ranges from at least 0.01 to 20 wt. %, preferably 0.1to 10 wt. %, and most preferably 0.5 to 4 wt. % based on the totalweight of the effect pigment.

One of the advantages of the present black effect pigment is the atleast partial SnO₂ or at least partial hydrated SnO₂ coating onto thesubstrate, especially mica or synthetic mica, provides a much improvedsubstrate surface for application of the adjacent Fe₃O₄ layer orcoating. This results in a greater amount of the Fe₃O₄ adhering to theplaty substrate rather than as Fe₃O₄ particle unassociated with thesubstrate. This gives a truer, deeper black effect pigment with littleor no staining issues and an effect pigment which is effective at lowerconcentrations.

Various tin salts may be used as the source of the tin oxide and/or tinoxide hydrate compound and both stannous and stannic salts areapplicable. It is characteristic of many tin salts that the solutionsreadily hydrolyze on dilution to form highly colloidal suspensions whichare positively charged. Insolubilization of the nucleating surface oftin oxide compound is readily effected by the heat, either by drying theisolated flakes or by heating the slurry to relatively hightemperatures.

Fe₃O₄

The magnetite layer or Fe₃O₄ layer can be deposited on a suitable platysubstrate either directly by wet chemical method, Chemical VaporDeposition (CVD), Physical Vapor Deposition (PVD). Alternatively, theplaty substrate can first be coated with iron(III) oxide which issubsequently reduced to a layer containing iron(II) oxide.

It is important to note that when Fe₃O₄ forms or deposits onto thesubstrate, small amounts of ferric hydroxide and Fe₂O₃ form and willlikely also be present.

Typically the Fe₃O₄ coating ranges from about 20 to about 70 wt. %,preferably about 25 to about 65 wt. %, about 35 to about 60 wt. % of thetotal weight of the inventive black effect pigment.

The SnO₂ and/or hydrated SnO₂ layer(s) and/or the Fe₃O₄ layer(s) mayencapsulate or form a continuous coating(s) or layer(s) on thesubstrate. It is not necessary that the tin oxide and iron oxidecoatings be partial.

Metal Oxide Coating

Another embodiment of the invention is the adherence of the Fe₃O₄ on thesurface of the substrate may be further improved using an additionalmetal oxide coating. This coating may function as an outer protectivelayer for the inner Fe₃O₄ layer or layers protecting the Fe₃O₄ layersfrom removal upon shear. This further metal oxide coating may alsoprotect the Fe₃O₄ from further oxidation.

Additionally the metal oxide layer evens the underlying Fe₃O₄ layer(s)making the effect pigment more suited to skin and cosmetic applications.

This optional protective layer may be selected from virtually any metaloxide, preferably a transparent metal oxide. For example, metal oxidessuch as SiO₂, TiO₂, ZrO₂, Al₂O₃ and ZnO₂ are envisioned.

A preferred embodiment for the optional metal oxide layer c) is a metaloxide selected from the group consisting of SiO₂, TiO₂ and ZnO₂,especially SiO₂ and TiO₂ and most especially SiO₂.

This optional protective layer or metal oxide outer layer may range fromabout 1 nm to about 350 nm, preferably about 5 nm to about 100 nm andespecially 10 to about 100 nm.

Although the embodiments discussed so far are the three layers, a) theSnO₂ or hydrated SnO₂ layer or coating, b) the Fe₃O₄ layer or coatingand c) the metal oxide layer, the inventive black effect pigment is notlimited to these three layers. Other variations are possible. Forexample interference pigments of the following layer sequences areenvisioned but not limited to:

substrate/SnO₂ and/or SnO₂ hydrate+Fe₃O₄(in same layer)

substrate/SnO₂ and/or SnO₂ hydrate+Fe₃O₄(in same layer)/SiO₂

substrate/SnO₂ and/or SnO₂ hydrate/Fe₃O₄

substrate/SnO₂ and/or SnO₂ hydrate/Fe₃O₄/SiO₂

substrate/SnO₂ and/or SnO₂ hydrate/Fe₃O₄/TiO₂

substrate/SnO₂ and/or SnO₂ hydrate/Fe₃O₄/ZnO₂

substrate/SnO₂ and/or SnO₂ hydrate/Fe₃O₄/ZrO₂

substrate/TiO₂+SnO₂/Fe₃O₄/SiO₂

substrate/SnO₂ and/or SnO₂ hydrate/TiO₂+SnO₂/Fe₃O₄/SiO₂

substrate/TiO₂+SnO₂/SnO₂ and/or SnO₂ hydrate/Fe₃O₄/SiO₂

substrate/SnO₂ and/or SnO₂ hydrate/Fe₃O₄/TiO₂+SnO₂/Fe₃O₄/SiO₂

substrate/SnO₂ and/or SnO2 hydrate/Fe₃O₄/SiO₂/SnO₂/Fe₃O₄/SiO₂

substrate/SiO₂/SnO₂ and/or SnO₂ hydrate/Fe₃O₄/TiO₂

substrate/SnO₂/TiO₂/SnO₂/Fe₃O₄/SiO₂

As indicated above, the inventive black pigment also embodies SnO₂ andFe₃O₄ present in one layer or the SnO₂ and Fe₃O₄ present in two separatelayers.

Preparation of the Black Effect Pigment

An effect pigment useful in the claimed pigment composition can beformed by any process known in the art. It can be accomplished, as oneexample, by precipitating a metal oxide onto laminar platy substrateparticulate and thereafter calcining the coated particulates to providemetal oxide-coated flake-form pigment.

In general, the procedure for preparing effect pigments involvesdispersing the substrate, especially a platy substrate and combiningthat dispersion with a precursor, which results in the deposition of anoxide of the precursor onto the substrate. For instance, in the case oftitanium oxide, titanyl chloride or titanium tetrachloride can be usedas the precursors. In the case of iron oxide, the precursor sourcematerial can be ferrous sulfate and in the case of tin oxide and/orhydrates thereof the precursor can be SnCl₂. The pH of the resultingslurry is maintained at an appropriate level during the addition of theiron salts by the use of a suitable base such as sodium hydroxide inorder to cause precipitation of the iron oxide(s) on to the platysubstrate. If desired, additional layers of titanium oxide, siliconoxide, SnO₂ and Iron oxide (or other metals) can be depositedsequentially.

Other coating procedures, such as for example, chemical vapordeposition(CVD) or physical vapor deposition processes (PVD), can alsobe used to prepare effect pigments useful in the claimed composition.

Accordingly the method of preparing the substantially black effectpigment comprises the steps of

-   -   applying a coating or layer of Fe₃O₄ onto an at least partially        coated or layered SnO₂ or hydrated SnO₂ coated substrate and        optionally applying a further metal oxide coating.

Wet chemical methods are of particular importance. The substrate isnormally suspended or dispersed in a liquid, especially water with oneor more hydrolysable metal salts being added at a pH which is suitablefor hydrolysis. The pH is selected in such a way that the metal oxidesor metal oxide hydrates are precipitated directly onto the flakeswithout secondary precipitations occurring. The pH can be kept constantby simultaneous metering-in of a base of acid.

In the case of the inventive black effect pigment, the SnO₂ and/or SOO₂hydrate treated platy substrate may be dispersed in a liquid in thepresence of a hydrolysable iron salt such as FeSO₄ at a basic pH with orwithout reducing conditions.

The precipitation of SnO₂ and/or SnO₂ hydrates onto the platy substratemay be carried out separately with drying or calcination followed byformation of a Fe₃O₄ layer. Alternatively, the tin oxide and/or hydratesthereof coating may be applied under acidic conditions in a first stepwithout drying or calcination followed by deposition of the Fe₃O₄ underbasic reducing or non-reducing conditions.

The invention is directed also to a novel method or use of improving theadhesion of Fe₃O₄ to a platy substrate, for example mica or syntheticmica.

The method entails increasing the adhesion of Fe₃O₄ to a substratecomprising the steps of

-   -   a) at least partially coating the substrate, especially mica        (synthetic or natural), with SnO₂ and/or hydrated SnO₂    -   b) applying Fe₃O₄ to the at least partially coated substrate of        step a) and    -   c) optionally, applying a further metal oxide coating, wherein        the partial layer of Fe₃O₄ may further contain ferric hydroxide        and Fe₂O₃.

The inventive black effect pigment may be further coated to give theeffect pigment a hydrophobic or hydrophilic character. Such treatmentmay improve formulation compatibility or improve the feel or touch ofthe pigments on skin. For example, U.S. published application no.2008/0213322 describes the coating of effect pigments withcetydimethicone to increase the hydrophobicity of the pigment. Otherexamples of hydrophobic treatment would include treatment of the pigmentwith cyclotetradimethylsiloxane, cyclopentadimethylsiloxane,cyclohexadimethylsiloxane, cyclocopolymer ofdimethylsiloxane/methyloctylsiloxane, hexylheptamethyltrisiloxane,lauroyl lysine and octylheptamethyltrisiloxane to name just a few of thepossible coating agents.

Applications of the Inventive Black Effect Pigment

The effect pigments according to the invention can be used for allcustomary purposes, for example for coloring polymers in the mass,coatings (including effect finishes, including those for the automotivesector) and printing inks (including offset printing, intaglio printing,gravure, bronzing and flexographic printing), and also for applicationsin cosmetics, in ink-jet-printing, for dyeing textiles, as well as lasermarking of papers and plastics. Such applications are known fromreference works, for example “Industrielle Organische Pigmente” (W.Herbst and K. Hunger, VCH Verlagsgesellschaft mbH, Weinheim/New York,2^(nd), completely revised edition, 1995).

A paint, coating, printing ink, plastic, cosmetic formulation, lasermarking, pigment composition or dry preparation, especially a cosmeticformulation comprising the inventive black effect pigment are importantembodiments of the present disclosure.

In one embodiment, the composition is part of a cosmetic composition.The form of the cosmetic composition can be any form normally used forcosmetics such as cream, emulsion, foam, gel, lotion, milk, mousse,ointment, paste, powder, spray, or suspension. The cosmetic compositioncan be any colored cosmetic used on the skin, hair, eyes, or lips, suchas concealing sticks, foundation, stage make-up, mascara (cake orcream), eye shadow (liquid, pomade, powder, stick, pressed or cream),hair color, lipsticks, lip gloss, kohl pencils, eye liners, blushers,eyebrow pencils, and cream powders. Other exemplary cosmeticcompositions include, but are not limited to, nail enamel, skin glosserstick, hair sprays, face powder, leg-makeup, insect repellent lotion,nail enamel remover, perfume lotion, and shampoos of all types (gel orliquid). In addition, the claimed compositions can be used in shavingcream (concentrate for aerosol, brushless, lathering), hair groom,cologne stick, cologne, cologne emollient, bubble bath, body lotion(moisturizing, cleansing, analgesic, astringent), after shave lotion,after bath milk and sunscreen lotion. For a review of cosmeticapplications, see Cosmetics: Science and Technology, 2nd Ed., Eds: M. S.Balsam and Edward Sagarin, Wiley-Interscience (1972) and deNavarre, TheChemistry and Science of Cosmetics, 2nd Ed., Vols 1 and 2 (1962), VanNostrand Co. Inc., Vols 3 and 4 (1975), Continental Press, both of whichare hereby incorporated by reference.

The cosmetic composition optionally comprises at least one cosmeticallyacceptable auxiliary agent. Cosmetically acceptable auxiliary agentsinclude, but are not limited to, carriers, excipients, emulsifiers,surfactants, preservatives, fragrances, perfume oils, thickeners,polymers, gel formers, dyes, absorption pigments, photo protectiveagents, consistency regulators, antioxidants, antifoams, antistats,resins, solvents, solubility promoters, neutralizing agents,stabilizers, sterilizing agents, propellants, drying agents, opacifiers,cosmetically active ingredients, hair polymers, hair and skinconditioners, graft polymers, water-soluble or dispersiblesilicone-containing polymers, bleaches, care agents, colorants, tintingagents, tanning agents, humectants, refatting agents, collagen, proteinhydrolyzates, lipids, emollients and softeners, tinting agents, tanningagents, bleaches, keratin-hardening substances, antimicrobial activeingredients, photofilter active ingredients, repellant activeingredients, hyperemic substances, keratolytic and keratoplasticsubstances, antidandruff active ingredients, antiphlogistics,keratinizing substances, active ingredients which act as antioxidantsand/or as free-radical scavengers, skin moisturizing or humectantssubstances, refatting active ingredients, deodorizing activeingredients, sebostatic active ingredients, plant extracts,antierythematous or antiallergic active ingredients and mixturesthereof. Cosmetic formulations are known in the art. See, for instance,US Publication Nos. 20080196847 and 20100322981.

The inventive black effect pigment may be added in any tinctoriallyeffective amount to the paint, coating, printing ink, high molecularweight organic material, cosmetic formulation, laser marking, pigmentcomposition or dry preparation.

The black effect pigment may be added to such materials as paint,coating, printing ink, high molecular weight organic material, cosmeticformulation, laser marking, pigment composition or dry preparation atconcentrations ranging for 0.0001 to about 90 wt. %, for example about0.001 to about 80 wt. %, especially 0.01 to about 50 wt. % wherein thewt. % is based on the total weight of the material.

In regard to cosmetic formulations the inventive black effect pigmentmay be added from about 0.0001 to 90 wt. % based on the total weight ofthe cosmetic formulation. The cosmetic formulation most likely willfurther contains a cosmetically suitable carrier material ranging fromabout 10 to about 90 wt. %. The cosmetically suitable carrier materialis preferably different than water.

EXAMPLES

The compositions and methods of use are further described in detail byreference to the following experimental examples. These examples areprovided for purposes of illustration only, and are not intended to belimiting unless otherwise specified. Thus, the compositions and methodsof use should in no way be construed as being limited to the followingexamples, but rather, should be construed to encompass any and allvariations which become evident as a result of the teaching providedherein.

Example 1

100 g of natural mica is slurried in 1000 ml of distilled water in a 3 lL flask. Slurry is stirred to keep homogeneous and heated to 82° C. ThepH is adjusted to 1.4 with HCl. SnCl₄ is added at controlled rate andthe pH is held at 1.4 with NaOH. After addition, stirring is continued30-60 minutes. Slurry can be cooled, filtered, washed and calcined, thenre-slurried in 1000 ml distilled water. The slurry is again stirred andheated to 85° C., pH adjusted to 8.2, and NaNO₃ is added. N₂ is bubbledthrough the slurry to purge oxygen. FeSO₄ (acidified) solution is pumpedin at controlled rate. The pH is controlled at 8.2 with NaOH. A sampleis removed, vacuum filtered, washed, dried and evaluated.

Example 2

100 g of synthetic mica is slurried in 1000 ml of distilled water in a 3l L flask. Slurry is stirred to keep homogeneous. The pH is adjusted to1.6 with HCl. SnCl₄ is added at controlled rate and the pH is held at1.6 with NaOH. After addition, stirring is continued 30-60 minutes. Theslurry is heated to 85° C., pH adjusted to 8.2, N₂ is bubbled throughthe slurry and NaNO₃ is added. FeSO₄ (acidified) solution is pumped inat controlled rate. The pH is controlled at 8.2 with NaOH. A sample isremoved, vacuum filtered, washed, dried and evaluated.

Example 3

100 g of synthetic mica is slurried in 1000 ml of distilled water in a 3l L flask. Slurry is stirred to keep homogeneous and heated to 85° C.The pH is adjusted to 1.6 with HCl. SnCl₄ is added at controlled rateand the pH is held at 1.6 with NaOH. After addition, stirring iscontinued 30-60 minutes. The slurry is cooled, filtered, rinsed andcalcined. The powder is reslurried, stirred, heated to 85° C., pHadjusted to 8.2, N₂ is bubbled and NaNO₃ is added. FeSO₄ (acidified)solution is pumped in at controlled rate. The pH is controlled at 8.2with NaOH. A sample is removed, vacuum filtered, washed, dried andevaluated. To encapsulate the Fe3O₄ to the surface, a metal oxide layercan be deposited over the Fe₃O₄. 20% sodium meta silicate can be addedat pH 8.0, temperature of 72° C. and pH balanced with HCl, or TiOCl₂ canbe added at pH 1.4-2.2 and pH balanced with NaOH to form TiO₂.

Example 4

100 g of natural mica is slurried in 1000 ml of distilled water in a 3 lL flask. Slurry is stirred to keep homogeneous and heated to 82° C. ThepH is adjusted to 1.4 with HCl. SnCl₄ is added at controlled rate andthe pH is held at 1.4 with NaOH. after addition, stirring is continued30-60 minutes. The slurry is heated to 85° C., pH adjusted to 8.2, NaNO₃is added, and then FeSO₄ (acidified) solution is pumped in. The pH iscontrolled at 8.2 with NaOH. A sample is removed, vacuum filtered,washed, dried and evaluated. To encapsulate the Fe₃O₄ to the surface, ametal oxide layer can be deposited over the Fe₃O₄. 20% sodium metalsilicate can be added at pH 8.0, temperature of 72° C. and pH balancedwith HCl, or TiOCl₂ can be added at pH 1.4-2.2 and pH balanced withNaOH.

Example 5 Comparative

100 g of natural mica is slurried in 1000 ml of distilled water in a 3 lL flask. The slurry is heated to 85° C., pH adjusted to 8.2, NaNO₃ isadded, and then FeSO₄ (acidified) solution is pumped in. The pH iscontrolled at 8.2 with NaOH. A sample is removed, vacuum filtered,washed, dried and evaluated.

Example 6

100 g of perlite is slurried in 1000 ml of distilled water in a 3 l Lflask. Slurry is stirred to keep homogeneous and heated to 82° C. The pHis adjusted to 1.4 with HCl. SnCl₄ is added at controlled rate and thepH is held at 1.4 with NaOH. After addition, stirring is continued 30-60minutes. Slurry can be cooled, filtered, washed and calcined, thenre-slurried in 1000 ml distilled water. The slurry is again stirred andheated to 85° C., pH adjusted to 8.2, and NaNO₃ is added. N₂ is bubbledthrough the slurry to purge oxygen. FeSO₄ (acidified) solution is pumpedin at controlled rate. The pH is controlled at 8.2 with NaOH. A sampleis removed, vacuum filtered, washed, dried and evaluated.

TABLE I Color measurements carried out on a X-Rite MA68II. Black WhiteParticle Size % FeSO4 SnO2 Example L C H L C h D₁₀ D₅₀ D₉₀ wt. % wt. % 136.09 1.62 275.69 44.81 0.91 288.64 9.893 20.683 38.88 2 36.4 4.63267.52 36.46 4.23 269.59 21.16 44.193 85.295 3¹ 40.54 2.16 272.66 43.091.96 270.88 32.796 66.129 120.522 4² 48.42 1.44 290.33 54.84 1.13 292.4722.725 48.553 92.353 37.46 1.78 4a³ 38.85 4.65 277.06 46.36 3.18 275.6136.085 73.153 133.432 5 31.42 2.18 274.75 37.06 0.95 330.17 8.804 19.42937.486 ¹Example 3 is substrate/SnO₂/Fe₃O₄/SiO₂ ²Example 4 issubstrate/SnO₂/Fe₃O₄/SiO₂ ³Example 4a is substrate/SnO₂/Fe₃O₄/TiO₂

APPLICATION EXAMPLES Pressed Eye Shadow Powder and Nail Enamel Drawdowns

Composition of Pressed Eye Shadow Powder

Ingredients Weight Fraction (%) Pressed Powder Base 59% Liquid binder 6.00 Black Pigment compositions¹ a-d 35.00

Composition of Nail Enamel Drawdowns

Phase Ingredient % w/w A Nail Enamel Base 94.00 UV absorbers q.s. BPigment 6.0

Procedure

Add phase A in an appropriate size vessel fitted with a propeller mixer.Add Phase B to Phase A mixing until batch is uniform.

Samples of Black Pigment Compositions

-   -   a) Inventive Black from Example 1 and 2 (mica/SnO2/˜38 wt. %        Fe3O4)-(JAS-0287-1). Synthetic mica (D10 is 20.77 microns, D50        is 44.84 microns, D90 is 81.45 microns)    -   b) Commercial Black Mica (mica/TiO₂/47-53% Fe₃O₄). (CLE-100052A)    -   c) Inventive Black but using Perlite as        substrate(pearlite/SnO₂/˜55% Fe₃O₄) (JAS-0286-1) The particle        size distribution for the perlite is D10 is 8.50, D50 is 24.32        and D90 is 52.68.    -   d) Synthetic Mica analog (CLM-100050A) is a mixture of 62 wt. %        synthetic mica and 38 wt. % Fe₃O₄. The synthetic mica particle        distribution is the same as a).    -   e) Inventive black pigment from synthetic mica/48% Fe₃O₄/SO₂    -   f) Inventive black pigment from natural mica/48% Fe₃O₄/SO₂

Results

Pressed Eye Shadow Powder Results and Nail Enamel Drawdowns

Inventive Blacks a) (JAS-0287-1), a), c), e) and f) when incorporatedinto either the pressed powder or the nail drawdown deliver adarker/stronger color in comparison to b) and d). This is quitesurprising in regard to b) as the Commercial Black Mica contain more wt.% Fe₃O₄. When d) is viewed side by side with the inventive black a), theinventive a) is also darker. Furthermore, the inventive blacks showbetter dispersibility when compared to analog d).

Additional Formulations Containing the Inventive Black

Body Splash Phase Ingredients % w/w A DI Water 28.70 Disodium EDTA 0.02Acrylates/C10-30 Alkyl Acrylate Crosspolymer (CARBOPOL ETD 2020)¹ (2%aqueous dispersion) 10.00 2-Amino 2-Methyl Propanol (amp-95)² 0.10Glycerin (and) Glyceryl Polyacrylate (HISPAGEL Oil, Low Viscosity)³ 2.00B Fragrance q.s Polysorbate 20 (and)PEG 40 Castor Oil 1.00 Glycereth-26(PROTACHEM GL-26)⁴ 1.00 Methylpropanediol (MP Diol Glycol)⁵ 2.00 CAlcohol (SD 39C) 55.00 Reflecks ™ Pinpoints of Pearl G130L(CalciumSodiumBorosilicate (and) TiO₂) 0.12 Chione ™ Snowfall White5130D(Synthetic Fluorphlogopite (and)TiO₂)⁶ 0.01 Inventive Black fromexamples 1, 3, 4 and/or 6 (Mica/SnO2/Fe3O4, 0.05 (Mica/SnO₂/Fe₃O₄/ SiO₂,Mica/SnO₂/Fe₃O₄/TiO₂, perlite/SnO₂/Fe₃O₄/SiO₂) Procedure I. Addingredients from Phase A in the order listed to the water at roomtemperature with moderate agitation And mix until uniform. Avoidaeration. II. Pre-mix Phase B-C separately at room temperature. CombinePhase B-C and add to Phase A with moderate agitation. Mix until uniform.Avoid aeration. Suppliers and Trademark Owners 1. The LubrizolCorporation  4. Protameen Chemicals Inc. 2. Dow Chemical Company  5.Lyondell Chemical Company 3. Hispano Quimica S.A./Centerchem, Inc  6.BASF Concealer Stick Phase Ingredients % w/w A Beeswax (WHITE BEESWAX)¹9.00 Hydrogenated Olive Oil/Olea Europaea (Olive) Fruit OilUnsaponifiables (OLIWAX)² 12.00 Copernicia Cerifera Wax (CARNAUBA T-3)¹3.00 Crambe Abyssinica Seed Oil and Shea Butter extract (FANCOR ABYSEA)³15.00 Meadowfoam Estolide (FANCOR MEADOWESTOLIDE)³ 3.00 Prunus AmygdalusDulcis Seed Oil (SWEET ALMOND OIL)⁴ 12.00 Ricinus Communis/SeedOil(CASTOR OIL)⁵ 6.00 Luvitol ® Lite (Hydrogenated Polyisobutene)⁶ 10.00B Crambe Abyssinica Seed Oil (FANCOR ABYSSINIAN OIL)³ 10.00Chroma-Lite ® Mauve CL4511 (Mica/Bismuth Oxychloride/Iron Oxides)⁶ 7.00Inventive Black from examples 1, 3, 4 and/or 6 (Mica/SnO2/Fe3O4, 3.00(Mica/SnO₂/Fe₃O₄/SiO₂, Mica/SnO₂/Fe₃O₄/TiO₂, perlite/SnO₂/Fe₃O₄/SiO₂)Chione ™ Snowfall White 5130D (Synthetic Fluorphlogopite/TiO₂)⁶ 5.00Desert Reflections ® Canyon Sunset 332D(Mica/TiO₂/iron Oxides) ⁶ 5.00Antioxidants q.s. Preservatives q.s. Procedure I. Pre-disperse Phase BII. Weigh all Phase A ingredients in a vessel and heat to 85 ± 3° C.,stirring until melted and uniform. III. Add premixed Phase B to Phase A,maintaining temperature at 82 ± 3° C. for 30 minutes with gentleagitation(This will allow de-aeration if vacuum is not available). IV.Reduce temperature to 75 ± 3° C. V. Pour into molds. Suppliers andTrademark Owners 1. Koster Keunen, LLC  4. Jeen InternationalCorporation 2. B&T Company  5. Alzo International Inc. 3. Fancor Ltd. 6. BASF Cream Foundation Phase Ingredients % w/w A DI Water (q.s to100%) 47.94 Methylpropanediol (mpdiol Glycol)¹ 5.00 Magnesium AluminumSilicate (VEEGUM)² 0.60 Xanthan Gum (KELTROL CG-T)³ 0.40 B CetearylOlivate/Sorbitan Olivate (OLIVEM 1000)⁴ 4.00 Hydrogenated Olive Oil/OleaEuropaea (Olive) Fruit Oil/Olea Europaea (Olive) 2.00 OilUnsaponifiables (OLIWAX)⁴ Caprylic/Capric Triglyceride/Di-PPG-3 MyristylEther Adipate/Sorbitan Isostearate 7.00 Meadowfoam Estolide/MeadowfoamDelta-Lactone(MEADOWDERM 100)⁶ 2.00 Isodecyl Neopentanoate (CERAPHYLSLK)⁷ 5.00 Antioxidants q.s. Preservatives q.s. C Kaolin (HUBER 90)⁸0.50 Polymethyl Methacrylate (PMMA H)⁹ 4.00 Titanium Dioxide 3.14Mearlmica ® SVA(Mica/Lauroyl Lysine)¹⁰ 3.00 Inventive Black fromexamples 1, 3, 4 and/or 6 (Mica/SnO2/Fe3O4, 0.12 (Mica/SnO₂/Fe₃O₄/SiO₂,Mica/SnO₂/Fe₃O₄/TiO₂, perlite/SnO₂/Fe₃O₄/SiO₂) D DI Water 10.00MultiReflections ™ Sunflower Sparkle 380P(Mica/TiO₂/SiO₂)¹⁰ 3.00Cloisonné ® Satin Rouge 450M (Mica/TiO₂/Iron oxides)¹⁰ 2.30 Procedure I.Add DI Water and MPDIOL Glycol to main vessel and begin homogenization.II. Sprinkle in VEEGUM and homogenize until uniform. III. Sprinkle inthe KELTROL CG-T and homogenize until uniform. IV. In a separatecontainer, heat Phase B to 60-70° C. and mix until uniform. V. Underhomogenization add Phase B to Phase A at 70° C. VI. Pulverize Phase C inappropriate blending equipment. VII. Under homogenization, sprinklePhase C to Phase AB until uniform color is achieved. Then, sweep mix.VIII. Premix Phase D and add to Phase ABC and begin cooling batch. IX.Drop batch at 40° C. Suppliers and Trademark Owners 1. Lyondell ChemicalCompany  6. Fancor Ltd. 2. RT Vanderbilt, Inc.  7. ISP 3. CP Kelco  8.J.M. Huber Corporation 4. B&T Company  9. Brenntag Specialties, Inc. 5.CRODA 10. BASF Deodorant Stick Phase Ingredients % w/w A DI Water (q.s.to 100%) 18.60 Propylene Glycol 59.20 PEG-200 Hydrogenated CastorOil/IPDI Copolymer (POLYDERM PPI-CO-200)¹ 12.00 Sodium Stearate (JEECHEMSodium Stearate)² 8.00 Isosteareth-2 (HETOXOL IS-2)³ 2.00 UV Absorbersq.s. B Inventive Black from examples 1, 3, 4 and/or 6 (Mica/SnO2/Fe3O4,0.10 (Mica/SnO₂/Fe₃O₄/SiO₂, Mica/SnO₂/Fe₃O₄/TiO₂,perlite/SnO₂/Fe₃O₄/SiO₂) Cellini ® Green 820CGBYF (Mica/TiO2 + Blue 1Lake + Yellow 5 Lake + 0.10 Hydrogenated Polyisobutene + Palmitic Acid 4C Fragrance q.s Procedure I. Mix Propylene Glycol and water and heat to80-85o C. II. Add Polyderm in small increments until all is melted anddissolved. III. Add Sodium Stearate and maintain temperature at 85o C.until solution is clear. IV. Add Isosteareth-2 Alcohol and mix well. V.Pre-disperse Phase B and add to Phase A. VI. Add Phase C to Phase A-Band mix until uniform. VII. Fill into appropriate containers Suppliersand Trademark Owners 1. Alzo International Inc.  3. Global Seven Inc. 2.Jeen International Corporation  4. BASF Eyeliner Phase Ingredients % w/wA. DI Water (q.s to 100%) 45.00 Luviset ®Clear(VP/Methacrylamide/VinylImidazole Copolymer) ¹ 20.00 D-Panthenol 75W (Panthenol) ¹ 1.00 Glycerin(and) Glyceryl Acrylate/Acrylic Acid Copolymer (and) Propylene Glycol(and) 10.00 PVM/MA Copolymer (LUBRAJEL OIL) ² Antioxidants q.s.Preservatives q.s. B Xanthan Gum (KELTROL CG-T) ³ 1.50 C DI Water 11.25Pearlescent and iridescent pigments Inventive Black from examples 1, 3,4 and/or 6 (Mica/SnO2/Fe3O4, 1.25 (Mica/SnO₂/Fe₃O₄/SiO₂,Mica/SnO₂/Fe₃O₄/TiO₂, perlite/SnO₂/Fe₃O₄/SiO₂) Reflecks ™ DimensionsShimmering Red G430Z 10.00 (Calcium Sodium Borosilicate (and) TitaniumDioxide) ¹ Procedure I. In a suitable container add all Phase Aingredients. II. Sprinkle Phase B into Phase A while being rapidlyagitated. III. Premix Phase C and add to Phase AB. *Note Cold process.Suppliers and Trademark Owners 1. BASF  3. CP Kelco 2. ISP Hair GlossPhase Ingredients % w/w A PEG-7 Glyceryl Cocoate (TEGOSOFT GC) ² 8.00Cremophor ® A 25 (Ceteareth-25) ¹ 22.00 Cremophor ® WO 7 (PEG-7Hydrogenated Castor Oil) ¹ 1.00 Propylene Glycol 3.00 PEG-8 Methicone(MASIL SF 19 CG) ³ 1.00 Pearlescent and iridescent pigments InventiveBlack from examples 1, 3, 4 and/or 6 (Mica/SnO2/Fe3O4, 0.05(Mica/SnO₂/Fe₃O₄/SiO₂, Mica/SnO₂/Fe₃O₄/TiO₂, perlite/SnO₂/Fe₃O₄/SiO₂) BDI Water (q.s to 100%) 64.85 C Fragrance (VERBENA MINT YY06-01079) ⁴0.10 Preservatives q.s. Procedure I Add Phase A ingredients in aboveorder at 80° C. and mix until uniform. Assure each is dissolved prior tonext addition. II. Heat Phase B to 80° C. and combine with Phase A. III.Cool to 50° C. while allowing air bubbles to rise out and foam todissolve. Add fragrance and preservative. IV. Pour into containers whileliquid and allow to set at room temperature. Suppliers and TrademarkOwners 1. BASF  3. The Lubrizol Corporation 2. Evonik Goldschmidt GmbH 4. Ungerer & Company Icy Gel Toothpaste Phase Ingredients % w/w A DIWater (q.s. to 100%) 6.25 Sorbitol (LIPONIC 70-NC) ¹ 54.30 Glycerin10.00 Cellulose Gum 0.50 PEG-32 (CARBOWAX PEG 1450) ² 3.00 B DI Water5.00 Sodium Benzoate 0.30 Sodium Saccharin 0.20 C Hydrated Silica(ZEODENT 165) ³ 5.00 Hydrated Silica (ZEODENT 113) ³ 15.00 D Flavor(Sweet Mint # 26037G) ⁴ 0.15 Blue 1 (0.5% Aqueous Solution) 0.10Pearlescent and iridescent pigments Inventive Black from examples 1, 3,4 and/or 6 (Mica/SnO2/Fe3O4, 0.20 (Mica/SnO₂/Fe₃O₄/SiO₂,Mica/SnO₂/Fe₃O₄/TiO₂, perlite/SnO₂/Fe₃O₄/SiO₂) Procedure I. Pre-mixWater, Sorbitol and Glycerin, and disperse Cellulose Gum with mixinguntil thoroughly dispersed. II. Add PEG-32 and heat to 50o C. III. At40o C. add pre-mixed Phase B to Phase A while mixing until completelyuniform. IV. Add Phase C to Phase A-B while under agitation. V. AddPhase D ingredients one by one to Phase A-B-C mixing until completelyuniform. VI. Fill into appropriate containers Suppliers and TrademarkOwners 1. Lipo Chemicals, Inc.  4. Shaw Mudge & Company 2. Dow ChemicalCompany  5. BASF 3. J.M Huber Corporation Lip Balm Phase Ingredients %w/w A Pentaerythrityl Tetraisostearate (CRODAMOL PTIS) - (q.s to 100%)20.05 Ricinus Communis (Castor) Seed Oil 11.60 Di-PPG-3 Myristyl EtherAdipate (CROMOLLIENT DP3A) ¹ 11.50 Crambe Abyssinica Seed Oil (FANCORABYSSINIAN OIL) ² 10.50 C10-30 Cholesterol/Lanosterol Esters (SUPERSTEROL ESTER) ¹ 6.25 Meadowfoam Estolide (MEADOWESTOLIDE) 2 6.00Meadowfoam Estolide (and) Meadowfoam Delta-Lactone (and) CrambeAbyssinica Seed 5.00 Oil (and) Carthamus Tinctorius (Safflower) Seed Oil(and) Olive Oil Unsaponifiable (and) Beta-Sitosterol (ANTI-AGING SKINCOMPLEX) ² Euphorbia Cerifera (Candelilla) Wax (Candelilla Wax SP 75) ³8.00 Copernicia Cerifera (Carnauba) Wax (Carnauba Wax SP 63) ³ 2.00Ozokerite (Ozokerite Wax White SP 1026) ³ 3.00 Microcrystalline Wax(MULTIWAX 180-W) ³ 3.00 Antioxidants q.s. Preservatives q.s. Fragranceq.s. Uvinul ® MC80 (Octinoxate) ⁴ 5.00 Oxybenzone 4.00 B Red 6* 0.10Pearlescent and iridescent pigments Inventive Black from examples 1, 3,4 and/or 6 (Mica/SnO2/Fe3O4, 4.00 (Mica/SnO₂/Fe₃O₄/SiO₂,Mica/SnO₂/Fe₃O₄/TiO₂, perlite/SnO₂/Fe₃O₄/SiO₂) C Fragrance q.s ProcedureI. Weigh all of Phase A ingredients in a vessel and heat to 85 ± 3° C.,stirring until melted and uniform. II. Add premixed Phase B to Phase Amaintaining temperature at 82 ± 3° C. for 30 minutes with gentleagitation. (This will allow de-aeration if vacuum is not available).III. Cool to 75 ± 3° C. and add fragrance and pour into container.*Note: If iron oxide or organic pigments are used, they should first bedispersed in Ricinus Communis (Castor) Seed Oil; this mixture shouldthen be milled in either a colloid or roller mill. Suppliers andTrademark Owners 1. CRODA  3. Strahl & Pitsch, Inc. 2. Fancor Ltd.  4.BASF Lipstick Phase Ingredients % w/w A Crambe Abyssinica Seed Oil(FANCOR ABYSSINIAN OIL⁾ ¹ (q.s to 100%) 34.86 Euphorbia Cerifera(Candelilla) Wax (Candelilla Wax SP 75) ² 3.00 Copernicia Cerifera(Carnauba) Wax (Carnauba Wax SP 63) ² 1.50 Beeswax (Beeswax White SP422) ² 1.00 Ceresine (Ceresine Wax White SP 252) ² 6.00 MicrocrystallineWax (MULTIWAX 180-W) ² 1.50 Oleyl Alcohol (NOVOL) ³ 3.00 IsosterylPalmitate (JEECHEM ISP) ⁴ 4.25 Caprylic/Capric Triglyceride 8.25Bis-Diglyceryl Polyacyladipate-2 (SOFTISAN 649) ⁵ 2.00 AcetylatedLanolin Alcohol (JEELAN MOD) ⁴ 2.50 Sorbitan Tristearate (JEECHEM STS) ⁴1.75 Ozokerite (Ozokerite Wax White SP 1026) ² 6.75 Glyceryl Monolaurate(ULTRAPURE GML) ⁶ 1.00 Antioxidants q.s. Preservatives q.s. UV Absorbersq.s. B Meadowfoam Estolide (MEADOWESTOLIDE) ² 2.00 Red 6 Lake * 3.14Pentaerythrityl Tetraisostearate (CRODAMOL PTIS) ³ 6.00 Chione ™Snowfall White S130D (Synthetic Fluorphlogopite (and) Titanium Dioxide)⁷ 9.00 Pearlescent and iridescent pigments Inventive Black from examples1, 3, 4 and/or 6 (Mica/SnO2/Fe3O4, 2.00 (Mica/SnO₂/Fe₃O₄/SiO₂,Mica/SnO₂/Fe₃O₄/TiO₂, perlite/SnO₂/Fe₃O₄/SiO₂) C Ethylhexyl Palmitate0.20 Biju ® Ultra UFC (Bismuth Oxychloride) ⁷ 0.30 D Fragrance q.s.Procedure I. Weigh all of Phase A ingredients in a vessel and heat to 85± 3° C., stirring until melted and uniform. II. Add premixed Phase B toPhase A, maintaining temperature at 82 ± 3° C. for 30 minutes withgentle agitation. III. Pre-disperse Biju ® Ultra UFC inEthylhexylpalmitate and add to Phase AB. IV. Cool to 75 ± 3° C. and addfragrance. V. Pour into container or components. *Note: If iron oxide ororganic pigments are used, they should first be dispersed in CrambeAbyssinica Seed Oil; this mixture should then be milled in either acolloid or roller mill. Supplies and Trademark Owners 1. Fancor Ltd.  5.SASOL 2. Strahl & Pitsch, Inc.  6. Ultra Chemical, Inc. 3. CRODA  7.BASF 4. Jeen International Corporation Eye Mascara Phase Ingredients %w/w A Caprylyl Methicone (DOW CORNING TORAY FZ-3196) ¹ 4.00 LaurylPEG/PPG-18/18 Methicone (DOW CORNING 5200 FORMULATION AID) ¹ 6.00Copernicia Cerifera (Carnauba) Wax (No. 1 Yellow Carnauba Wax) ² 3.00C30-45 Alkyldimethylsilyl Polypropylsilsesquioxane 2.00 (DOW CORNINGSW-8005 C30 RESIN WAX) ¹ Caprylic/Capric Triglyceride (JEECHEM CTG) ³3.00 Uvinul ® A Plus B* (Ethylhexyl Methoxycinnamate (and) 0.10Diethylamino Hydroxybenzoyl Hexyl Benzoate) ⁴ Preservatives O/S q.s.Vitamin E Acetate Care (Tocopheryl Acetate ) ⁴ 0.25 B Isododecane(Permethyl 99A) ⁵ (q.s to 100%) 25.00 Isododecane (and) DisteardimoniumHectorite (and) Propylene Carbonate 6.00 (BENTONE GEL ISD V) ⁶Polymethyl Methacrylate (PMMA S) ⁷ 5.00 C Pearlescent and iridescentpigments Inventive Black from examples 1, 3, 4 and/or 6(Mica/SnO2/Fe3O4, 2.00 (Mica/SnO₂/Fe₃O₄/SiO₂, Mica/SnO₂/Fe₃O₄/TiO₂,perlite/SnO₂/Fe₃O₄/SiO₂) Reflecks ™ Dimensions Luminous Gold G230M 4.00(Calcium Sodium Borosilicate (and) Titanium Dioxide) ⁴ DI Water 17.65Propylene Glycol 2.00 Preservatives W/S q.s. D Luviset ® Shape(Polyacrylate-22) ⁴ 20.00 Procedure I. In main vessel heat Phase Aingredients to 60° C. with continuous mixing. II. In a side vesselpremix Phase B into Phase A maintaining temperature to 60° C. ** Note:Black 2 should first be dispersed in Isododecane; this mixture shouldthen be milled in either a colloid or roller mill. III. In a side vesselpremix Phase C and heat to 50° C. IV. Add Phase C to Phase AB underhomogenization. Sweep mix and reduce heat to 50° C. V. Add Phase D toPhase ABC. VI. Package into appropriate containers. * Uvinul ® A Plus Bis not an approved Sunscreen active in the USA & Canada. ** When CarbonBlack pigments are used, they should first be dispersed in Isododecaneand BENTONE Gel ISD V this mixture should then be milled in either acolloid or roller mill. Suppliers and Trademark Owners 1. Dow CorningCorporation  5. Presperse LLC 2. Frank B. Ross Company, Inc.  6.Elementis Specialties 3. Jeen International Corporation  7. BrenntagSpecialties Inc. 4. BASF Nail Enamel Phase Ingredients % w/w A NailEnamel Base (Butyl Acetate (and) Toluene (and) Nitrocellulose 97.90(and) Tosylamide/Formaldehyde Resin (and) Isopropyl Alcohol (and)Dibutyl Phthalate (and) Ethyl Acetate (and) Camphor (and) n-ButylAlcohol (and) Silica (and) Quaterinum-18 Hectorite) B Red 6(10.50-15.50% Toluene Free/Formaldehyde Free Color Solution) 1.10Pearlescent and iridescent pigments Inventive Black from examples 1, 3,4 and/or 6 (Mica/SnO2/Fe3O4, 0.20 (Mica/SnO₂/Fe₃O₄/SiO₂,Mica/SnO₂/Fe₃O₄/TiO₂, perlite/SnO₂/Fe₃O₄/SiO₂) Gemtone ® Tan Opal G005(Mica (and) Titanium Dioxide (and) Iron Oxides) ¹ 0.80 Procedure I. AddPhase A in an appropriate size vessel fitted with a propeller mixer. II.Add Phase B to Phase A mixing until batch is uniform. III. Fill intocontainers. Suppliers and Trademark Owners 1. BASF Pressed Powder EyeShadow Phase Ingredients % w/w A Bi-Lite ® 20 (Mica (and) BismuthOxychloride) ¹ (q.s to 100%) 21.50 Kaolin (HUBER 90) ² 15.00Microcrystalline Cellulose (AVICEL PC 105) ³ 12.50 Pearlescent andiridescent pigments Inventive Black from examples 1, 3, 4 and/or 6(Mica/SnO2/Fe3O4, 9.50 (Mica/SnO₂/Fe₃O₄/SiO₂, Mica/SnO₂/Fe₃O₄/TiO₂,perlite/SnO₂/Fe₃O₄/SiO₂) Gemtone ® Tan Opal G005 (Mica (and) TitaniumDioxide (and) Iron Oxides) ¹ 28.50 B Crambe Abyssinica Seed Oil (and)Butyrospermum Parkii (Shea Butter) Extract 7.50 (FANCOL ABYSHEA) ⁴Simmondsia Chinensis (Jojoba) Seed Oil 1.50 Cocos Nucifera (Coconut) Oil1.00 Antioxidant q.s. Preservatives q.s. C Reflecks ™ DimensionsSparkling Blue G630D (Calcium Sodium Borosilicate 3.00 (and) TitaniumDioxide) ¹ Procedure I. Thoroughly blend Phase A in appropriate dryblending/dispersing equipment. II. Pre-disperse Phase B until uniform.III. Spray Phase B into Phase A. Pulverize and return to blender. IV.Add Phase C to Phase AB. Tumble until uniform. V. Press. Suppliers andTrademark Owners 1. BASF  3. FMC Corporation 2. J.M. Huber Corporation 4. Fancor Ltd. Shampoo Phase Ingredients % w/w A DI Water (q.s. to100%) 15.40 Acrylates/Aminoacrylates/C10-30 Alkyl PEG-20 ItaconateCopolymer (STRUCTURE PLUS) ₁ 7.00 B DI Water 15.00 Comperlan ®100(Cocamide MEA) ² 0.50 C Texapon ® NSO (Sodium Laureth Sulfate) ² 35.70Cocamidopropyl Betaine (TEGO BETAIN L 7) ³ 13.50 Disodium LaurethSulfosuccinate (REWOPOL SBFA 30B) ³ 7.80 Luviquat ® Sensation(Polyquaternium-87) ⁴ 1.84 Preservatives q.s. Fragrance (Spring Flower #0794029) ⁴ 0.500 Pearlescent and iridescent pigments Inventive Blackfrom examples 1, 3, 4 and/or 6 (Mica/SnO2/Fe3O4, 0.16(Mica/SnO₂/Fe₃O₄/SiO₂, Mica/SnO₂/Fe₃O₄/TiO₂, perlite/SnO₂/Fe₃O₄/SiO₂)Blue 1 (1% Aqueous Solution) 0.25 D Citric Acid (10% Aqueous Solution)2.35 Procedure I. Weight out components of Phase A and Phase Bseparately and stir until the solution is homogeneous. II. Add Phase Bto Phase A and stir until uniform. III. Add Phase C to Phase AB and stiruntil uniform. IV. Adjust pH to 5.6 with citric acid with constantstirring. Suppliers and Trademark Owners 1. National Starch & ChemicalCompany  3. Evonik Industries 2. BASF  4. Bell Flavors & Fragrances,Inc. Spray Highlighter Phase Ingredients % w/w A SD Alcohol 40 B(Alcohol Denatured) ² 55.00 Aminomethyl Propanol (AMP-95) ³ 0.88 MEABorate (and) MIPA Borate (MONACOR BE) ⁴ 0.05 Uvinul ® MC 80 (EthyhexylMethoxycinnamate) ¹ 0.05 Cyclopentasiloxane (DOW CORNING 245 Fluid) ⁵0.10 D-Panthenol 75W (Panthenol) ¹ 0.10 Cucumber TEA 862157 (Fragrance)⁶ 0.10 Luvimer ® 100P (Acrylates Copolymer) ¹ 2.00 Ultrahold ® Strong(Acrylates Copolymer) ¹ 3.00 B Chione ™ Snowfall White S130D (SyntheticFluorphlogopite (and) Titanium Dioxide) ⁷ 0.10 Pearlescent andiridescent pigments Inventive Black from examples 1, 3, 4 and/or 6(Mica/SnO2/Fe3O4, 0.90 (Mica/SnO₂/Fe₃O₄/SiO₂, Mica/SnO₂/Fe₃O₄/TiO₂,perlite/SnO₂/Fe₃O₄/SiO₂) C Hydroflourocarbon 152A ⁷ 37.72 Procedure I.Mix all ingredients in order shown with adequate agitation. II. Fillinto appropriate containers and charge with propellant. Aerosol Density:0.85 g/mL Vapor Pressure @ ambient: 55 psig Packaging Can: Exal AluminumEpoxy Lined Valve: Seaquist Perfect Valve XT-96 Body: XT ES BRB 013 ORIFN Stem: 0.013 Virgin Nylon Actuator: XT-150 ES 0.013 Misty Diptube:0.165 ID″ Suppliers and Trademark Owners 1. BASF  5. Dow CorningCorporation 2. AAPER Alcohol and Chemical Co.  6. Drom Fragrances, Inc.3. Dow Chemical Company  7. DuPont Company Elegant Sun Protection PhaseIngredients % w/w A DI Water 38.10 D-Panthenol 75W (Panthenol) ¹ 1.00Pluracare ® E 400 NF (PEG-8) ¹ 2.50 Edeta ® BD (Disodium EDTA) ¹ 0.10Luvigel ® STAR (Polyurethane-39) ¹ 2.50 B. Uvinul ® T 150*(Octyltriazone) ¹ 2.00 Tinosorb ® S* (Bemotrizinol) ¹ 3.00 Cetiol ®Sensoft (Propylheptyl Caprylate) ² 5.00 Cetiol ® CC (DicaprylylCarbonate) 5.00 C Cremophor ® A 25 (Ceteareth-25) ¹ 2.50 Cremophor ® GS32 (Polyglyceryl-3 Distearate) ¹ 2.50 Cremophor ® WO-7(PEG-7Hydrogenated Castor Oil) ¹ 0.50 Stearyl Alcohol (LANETTE 18) ² 2.50Dimethicone (DOW CORNING 200 FLUID 50 CST) ³ 1.50 Luvitol ® Lite(Hydrogenated Polyisobutene) ¹ 1.50 Vitamin E Acetate Care (TocopherolAcetate) ¹ 0.50 Bisabolol Racemic (Bisabolol) ¹ 1.00 D DI Water 10.00Tinosorb ® M* (Bisoctrizole) 10.00 E DI Water (q.s. to 100%) 5.50Cloisonné ® Satin Gold 262MC (Mica (and) Titanium Dioxide (and) IronOxides) 1.60 Pearlescent and iridescent pigments Inventive Black fromexamples 1, 3, 4 and/or 6 (Mica/SnO2/Fe3O4, 0.20 Mica/SnO₂/Fe₃O₄/SiO₂,Mica/SnO₂/Fe₃O₄/TiO₂, perlite/SnO₂/Fe₃0₄/SiO₂) Cloisonné ® Satin Bronze250M (Mica (and) Iron Oxides) ¹ 0.60 Cloisonné ® Satin Copper 350M (Mica(and) Iron Oxides) ¹ 0.20 F Fragrance (ORANGE NECTAR FRAG. AD78-00997) ⁴0.20 Preservatives q.s. * Note: Tinosorb S, Tinosorb M and Uvinul T 150are not an approved Sunscreen active in the USA and Canada. Procedure I.Combine Phase A and heat to 75-80° C. II. Pre-mix Phase B and heat to75-80° C. III. Combine Phase C and heat to 75-80° C. IV. Add Phase B toPhase C while at 75-80° C. and mix well. V. Add Phase BC to Phase A andhomogenize for 2-3 minutes while at 75-80° C. at low speed. VI. Transferto sweep mixing and start cooling. VII. Pre-mix Phase D and add to thebatch at 50° C. or below. VIII. Pre-mix Phase E and add to the batch,then mix well. IX. Add Phase F one by one and mix well, then stop.Suppliers and Trademark Owners 1. BASF  3. Dow Corning Corporation 2.COGNIS  4. Ungerer & Company Talc Free Mineral Bronzer Phase Ingredients% w/w A Mearlmica ® SVA (Mica (and) Lauroyl Lysine) ¹ (q.s. to 100%)36.500 Flamenco ® Sparkle Red 420J (Mica (and) Titanium Dioxide) ¹15.000 Z-Cote ® (Zinc Oxide) ¹ 15.000 Cloisonné ® Satin Bronze (Mica(and) Iron Oxides) ¹ 20.000 Pearlescent and iridescent pigmentsInventive Black from examples 1, 3, 4 and/or 6 (Mica/SnO2/Fe3O4, 3.500Mica/SnO₂/Fe₃O₄/SiO₂, Mica/SnO₂/Fe₃O₄/TiO₂, perlite/SnO₂/Fe₃O₄/SiO₂)Boron Nitride Powder (Boron Nitride) ² 5.000 B Luvitol ® Lite(Hydrogenated Polyisobutene) ¹ 2.500 Octyldodecyl Neopentanoate (ElefacI-205) ³ 2.500 Antioxidants q.s. Preservatives q.s. Procedure I.Thoroughly blend Phase A in appropriate dry blending/dispersingequipment. II. Pre-disperse Phase B and spray into Phase A. III.Pulverize and package into appropriate containers. Suppliers andTrademark Owners 1. BASF  3. Alzo International, Inc. 2. ESK Ceramics

While the compositions and their methods of use have been disclosed withreference to specific embodiments, it is apparent that other embodimentsand variations may be devised by others skilled in the art withoutdeparting from the true spirit and scope of the described compositions,kits and methods of use. The appended claims are intended to beconstrued to include all such embodiments and equivalent variations.

1. A black effect pigment comprising a) at least a partial layer of SnO₂and/or hydrated SnO₂ on a substrate, b) at least a partial layer ofFe₃O₄, and c) optionally, a further layer of metal oxide, wherein the atleast partial layer of Fe₃O₄ may further contain ferric hydroxide andFe₂O₃.
 2. The black effect pigment of claim 1, wherein the SnO₂ and/orhydrated SnO₂ layer and/or the Fe₃O₄ layer encapsulates or forms acontinuous coating or layer on the substrate.
 3. The pigment of claim 1,which further layer c) is selected from the metal oxide group consistingof SiO₂, TiO₂, ZrO₂, Al₂O₃ and ZnO₂.
 4. The pigment of claim 3, whereinthe metal oxide is SiO₂ or TiO₂.
 5. The pigment of claim 1, wherein thepigment contains a metal oxide layer c) and the metal oxide layer istransparent.
 6. The pigment of claim 1, wherein the substrate isselected from the group consisting of aluminum oxide, platy glass,perlite, aluminum, natural mica, synthetic mica, bismuth oxychloride,platy iron oxide, platy graphite, bronze, stainless steel, naturalpearl, boron nitride, silicon dioxide, copper flake, copper alloy flake,zinc flake, zinc alloy flake, zinc oxide, enamel, china clay, porcelain,titanium oxide, titanium dioxide, titanium suboxides, zeolite, kaolin,zeolites and combinations thereof.
 7. The pigment of claim 1, whereinthe substrate is selected from the group consisting of natural mica,synthetic mica, perlite, platy glass and aluminum.
 8. The pigment ofclaim 1, with the proviso that the SnO₂ and/or SnO₂ hydrate coating orlayer which impinges the Fe₃O₄ coating layer is not incorporated into aTiO₂ coating or layer.
 9. The pigment of claim 1, wherein the substrateis mica or synthetic mica.
 10. The pigment of claim 1, wherein the SnO₂and/or hydrated SnO₂ layer or layers range in weight from about 0.01 to20 wt. % SnO₂ and/or hydrated SnO₂ and the weight percent is based onthe total weight of the black effect pigment.
 11. The pigment of claim1, wherein the SnO₂ and Fe₃O₄ are present in the same layer.
 12. Thepigment of claim 1, wherein the SnO₂ and Fe₃O₄ are present in twoseparate layers.
 13. The pigment of claim 1, which has the followinglayer structure: substrate/SnO₂ and/or SnO₂ hydrate+Fe₃O₄(in same layer)substrate/SnO₂ and/or SnO₂ hydrate+Fe₃O₄(in same layer)/SiO₂substrate/SnO₂ and/or SnO₂ hydrate/Fe₃O₄ substrate/SnO₂ and/or SnO₂hydrate/Fe₃O₄/SiO₂ substrate/SnO₂ and/or SnO₂ hydrate/Fe₃O₄/TiO₂substrate/SnO₂ and/or SnO₂ hydrate/Fe₃O₄/ZnO₂ substrate/SnO₂ and/or SnO₂hydrate/Fe₃O₄/ZrO₂ substrate/TiO₂+SnO₂/Fe₃O₄/SiO₂ substrate/SnO₂ and/orSnO₂hydrate/TiO₂+SnO₂/Fe₃O₄/SiO₂ substrate/TiO₂+SnO₂/SnO₂ and/or SnO₂hydrate/Fe₃O₄/SiO₂ substrate/SnO₂ and/or SnO₂hydrate/Fe₃O₄/TiO₂+SnO₂/Fe₃O₄/SiO₂ substrate/SnO₂ and/or SnO2hydrate/Fe₃O₄/SiO₂/SnO₂/Fe₃O₄/SiO₂ substrate/SiO₂/SnO₂ and/or SnO₂hydrate/Fe₃O₄/TiO₂ substrate/SnO₂/TiO₂/SnO₂/Fe₃O₄/SiO₂, wherein thesubstrate is selected from the group consisting of aluminum oxide, platyglass, perlite, aluminum, natural mica, synthetic mica, bismuthoxychloride, platy iron oxide, platy graphite, bronze, stainless steel,natural pearl, boron nitride, silicon dioxide, copper flake, copperalloy flake, zinc flake, zinc alloy flake, zinc oxide, enamel, chinaclay, porcelain, titanium oxide, titanium dioxide, titanium suboxide,zeolite, kaolin, borosilicate and combinations thereof.
 14. A paint,coating, powder coating, printing ink, laser marking pigment, cosmeticformulation, pigment composition or dry preparation comprising the blackeffect pigment according to claim
 1. 15. A cosmetic formulationcomprising the black effect pigment according to claim
 1. 16. Thecosmetic formulation according to claim 15, which further contains fromabout 10 to about 90 wt. % a cosmetically suitable carrier material. 17.The cosmetic formulation according to claim 15, wherein the formulationis a cosmetic products selected from concealing sticks, foundations,stage make-up, mascaras (cake or cream), eye shadows (liquid, pomade,powder, stick, pressed or cream), hair color, lipsticks, lip gloss, kohlpencils, eye liners, blushers, eyebrow pencils, cream powders, nailenamels, skin glosser stick, hair sprays, face powders, leg-makeup,insect repellent lotion, nail enamel remover, perfume lotion, shampoosof all types (gel or liquid) shaving creams (concentrate for aerosol,brushless, lathering), hair grooming products, cologne sticks, colognes,cologne emollients, bubble baths, body lotions (moisturizing, cleansing,analgesic, astringent), after shave lotions, and after bath milks andsunscreen lotions.
 18. A method of preparing the black effect pigmentaccording to claim 1, comprising the steps of applying a coating orlayer of Fe₃O₄ which may further include ferric hydroxide or ferricoxide, onto an at least partially coated or layered SnO₂ which mayfurther include hydrated SnO₂ coated substrate and optionally applying afurther metal oxide coating.
 19. The method according to claim 18,wherein the substrate is selected from the group consisting of aluminumoxide, platy glass, perlite, aluminum, natural mica, synthetic mica,bismuth oxychloride, platy iron oxide, platy graphite, platy silica,bronze, stainless steel, natural pearl, boron nitride, copper flake,copper alloy flake, zinc flake, zinc alloy flake, zinc oxide, enamel,china clay, porcelain, titanium oxide, titanium dioxide, titaniumsuboxides, zeolites, kaolin and combinations thereof.
 20. A method ofincreasing the adhesion of Fe₃O₄ to a substrate comprising the steps ofa) at least partially coating the substrate with SnO₂ or hydrated SnO₂b) applying Fe₃O₄ to the at least partially coated substrate of step a)and c) optionally, applying a further metal oxide coating.